WO2010046211A1 - Method and device for operating a smelting reduction process - Google Patents
Method and device for operating a smelting reduction process Download PDFInfo
- Publication number
- WO2010046211A1 WO2010046211A1 PCT/EP2009/062607 EP2009062607W WO2010046211A1 WO 2010046211 A1 WO2010046211 A1 WO 2010046211A1 EP 2009062607 W EP2009062607 W EP 2009062607W WO 2010046211 A1 WO2010046211 A1 WO 2010046211A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- export
- turbine
- export gas
- supplied
- Prior art date
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/06—Making pig-iron in the blast furnace using top gas in the blast furnace process
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B7/00—Blast furnaces
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B7/00—Blast furnaces
- C21B7/002—Evacuating and treating of exhaust gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C6/00—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas- turbine plants for special use
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B1/00—Shaft or like vertical or substantially vertical furnaces
- F27B1/10—Details, accessories, or equipment peculiar to furnaces of these types
- F27B1/26—Arrangements of controlling devices
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/001—Extraction of waste gases, collection of fumes and hoods used therefor
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
- C21B2100/28—Increasing the gas reduction potential of recycled exhaust gases by separation
- C21B2100/282—Increasing the gas reduction potential of recycled exhaust gases by separation of carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
- C21B2100/62—Energy conversion other than by heat exchange, e.g. by use of exhaust gas in energy production
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Definitions
- the invention relates to a method for operating a smelting reduction process, in particular with a blast furnace or with a melting unit and at least one reduction unit, feedstocks, using carbon carriers and optionally additives, reduced by means of a reducing gas and melted into pig iron or steel precursors and the reacted reducing gas as Topgas derived and purified as export gas is discharged.
- the invention further relates to an apparatus for operating a smelting reduction process with a blast furnace, or with a smelting unit and at least one reduction unit, wherein feedstocks, using carbon carriers and optionally additives, reduced by means of a reducing gas and melted into pig iron or steel precursors and the reacted reducing gas derived as a top gas and purified, optionally mixed with purified and cooled excess gas from the smelting unit, can be removed as export gas.
- the export gas is thermally utilized in a gas turbine.
- the exhaust gas of this gas turbine is used in a waste heat steam generation for the production of steam.
- Another part of the export gas is fed to a device for the separation of CO 2 and / or the low-pressure export gas system, the resulting tail gas, ie the residual gas, which is formed by the deposition of CO 2 , the waste heat generated and burned for additional generation of steam ,
- the export gas is qualitatively improved by the means for separating CO 2 , while the reduction potential, ie the proportion of reducing components, raised or generates a high-quality reducing gas, which can be fed to a metallurgical use.
- the reduction gas quantity from the melter gasifier is not uniform, a control gas quantity, the so-called surplus gas, must be discharged as export gas.
- the amount of excess gas is due to a reduction gas required in the reduction unit as uniform as possible reduction gas and a system pressure control in the smelting unit.
- the top gas is withdrawn from the blast furnace or from the reduction unit.
- the export gas can be supplied to a gas turbine and thus the energy balance of the composite of a smelting reduction process and a gas turbine or a waste heat steam generation can be significantly improved.
- the purification of the top gas can take place by means of a dry separation, in particular a gravity separation, and / or a wet separation.
- the top gas is mostly dust laden, so that the dusts and fine solid particles must be separated.
- a dry separation offers the advantage that there is no strong cooling of the top gas.
- a complete removal of dusts and solid particles can be done by a wet dedusting, which can be followed by a dry dedusting or used alone.
- the dry or wet cleaned top gas is called export gas and can now be used in a turbine.
- the remaining part of the export gas is first compressed, cooled and then fed to the device for the separation of CO 2 .
- the process conditions for the separation of CO 2 can be adjusted or improved.
- the export gas is compressed prior to combustion in the gas turbine in a fuel gas compressor.
- the gas turbine can be set in an economically optimal operating point and the efficiency can be increased.
- a part of the export gas is fed to an expansion turbine, wherein it is depressurized and subsequently admixed with the tail gas.
- the turbine can be coupled to a generator for generating electricity.
- the expanded export gas is subsequently added to the tail gas, with the proportion of combustible components increasing overall.
- An advantageous embodiment of the method according to the invention provides that the tail gas, if appropriate after mixing with export gas, is temporarily stored in a storage device to compensate for fluctuations in the calorific value before it is burned in the waste heat steam generation. Due to the process, the device for the separation of CO 2 generates a tail gas, which has a large number of different calorific values, the fluctuations occurring at a high frequency, ie occurring only briefly in time and largely compensated for a long time. Thus, through a compensation in a caching set a nearly uniform calorific value and strong fluctuations in the combustion can be avoided. By adding export gas into the tail gas, the calorific value can be further adjusted.
- the export gas is dedusted before its combustion in the gas turbine.
- the additional dedusting ensures that residual dust does not damage the turbine.
- metallurgical gases and / or natural gas and / or nitrogen and / or water vapor or mixtures thereof are added.
- Gas turbines require a uniform heating capacity and a uniform calorific value for stable operation. Due to variations in the operation of the smelting reduction process, there are changes in the composition, so that the introduction of metallurgical gas according to the invention, such as e.g.
- Crucible gases or coke oven gas which is available in huts in sufficient quantities or other suitable combustible gases, the heating value can be increased if necessary or reduced by mixing nitrogen, so that stable conditions for the gas turbine can be ensured.
- Particularly cost is the use of waste nitrogen from an air separation plant
- the export gas is buffered before its combustion in the gas turbine in a buffer device in order to ensure a homogenization of the amount of export gas.
- the steam generated in the waste heat steam generation is fed to a steam turbine.
- a special embodiment of the method according to the invention provides that the device for the separation of CO 2 on the basis of a pressure-alternating or a vacuum pressure-exchange method, in particular on adsorption basis works. Such processes are characterized by high deposition rates, so that the purified export gas has a high reduction potential and can be used again in the smelting reduction process, whereby the amount of CO 2 produced per ton of pig iron can be reduced.
- An advantageous embodiment of the method according to the invention provides that only export gas with an average calorific value> 4000 kJ / Nm 3 , in particular> 5000 kJ / Nm 3 , the gas turbine is supplied.
- the calorific value of the export gas can be ensured that the gas turbine achieves a high efficiency, the dedusting, the buffer device, the fuel gas compressor can be made smaller, since export gas with a too low calorific value does not need to be supplied through these facilities of the turbine , This results in lower-cost components up to the gas turbine.
- the energy loss is avoided by the otherwise necessary compression of CO 2 rich tail gas and subsequent relaxation in the gas turbine.
- the calorific value of the export gas is determined online.
- a continuous regulation of the calorific value in particular by admixing combustible gases or nitrogen, is possible, whereby an even more stable operation of the gas turbine is made possible.
- the proportion of the export gas supplied to the gas turbine makes up 30 to 90% of the top gas. Based on this amount, on the one hand use of the combustible components of the export gas is possible, while still enough export gas of the device for the separation of CO 2 can be supplied, so that use in the smelting reduction process is possible.
- the shares can also be adjusted if necessary, for example, if more export gas is to be returned to the smelting reduction process.
- a particularly advantageous embodiment of the method according to the invention is achieved when the blast furnace is operated with an oxygen-containing gas, in particular with an oxygen content of> 70%, particularly preferably> 80%.
- an oxygen-containing gas in particular with an oxygen content of> 70%, particularly preferably> 80%.
- a suitable embodiment of the method according to the invention provides that at least part of the export gas purified in the device for separating off CO 2 , if appropriate after heating, is introduced into the blast furnace or the reduction unit.
- the export gas purified in this way has a high reduction potential and can therefore be used again to reduce the starting materials, so that, for example, the amount of carbon carriers in the blast furnace or in the reduction unit can be reduced.
- Typical starting materials are iron ores, agglomerated iron ore carriers (pellets, sinters), iron ore concentrates and additionally carbon carriers and additives.
- the export gas can be heated inexpensively to adjust the gas temperature necessary for the entry.
- the device according to the invention for operating the smelting reduction process according to the invention comprises a blast furnace, or a smelting unit and at least one reduction unit, wherein feedstocks, using carbon carriers and optionally additives, are reduced by means of a reducing gas and melted to form pig iron or steel precursors.
- the reduction gas reacted in the smelting reduction process is discharged and purified as a top gas, optionally mixed with purified and cooled excess gas from the smelting unit, removed as export gas.
- a gas turbine with a generator for the thermal conversion of at least a portion of the export gas and a waste heat steam generation are provided, in which by means of the hot exhaust gases from the gas turbine steam can be generated.
- the device according to the invention has a device for the separation of CO 2 , to which at least part of the remaining export gas can be supplied, to form a CO 2 -purified gas and a tail gas, and a storage device for receiving and compensating calorific value fluctuations in the tail gas, wherein the storage means is connected to the waste heat generation, which comprises a heater for burning the tail gas to form steam.
- the export gas which has a high pressure and a high calorific value, can be processed separately from the tail gas, which has a low pressure and a lower calorific value.
- the amount of high-quality export gas is lower, this is characterized by the higher pressure and the higher calorific value, so that its use in the gas turbine can be made more efficient.
- a steam turbine is provided with a generator for relaxing the steam produced in the waste heat steam generation.
- a dry separation device for cleaning the top gas, a dry separation device, in particular a gravity separation, and / or a wet separation device can be provided.
- the necessary purity of the export gas can be adjusted, the dry separation has the advantage of only a slight cooling of the top gas
- a buffer device for storing the export gas prior to its supply to the gas turbine, so that the gas turbine supplied export gas quantity or the export gas heating value can be kept uniform.
- the buffer device has a measuring device for measuring the calorific value of the export gas, based on the measurement for adjusting the calorific value of metallurgical gas and / or natural gas and / or nitrogen and / or water vapor can be supplied.
- a measuring device for measuring the calorific value of the export gas based on the measurement for adjusting the calorific value of metallurgical gas and / or natural gas and / or nitrogen and / or water vapor can be supplied.
- a regulation of the calorific value or the amount of export gas can be realized, wherein by means of actuators, such. Control valves, the amount of export gas or can be adjusted to mixed metallurgical gas and / or nitrogen.
- a filter in particular an electrostatic filter, is provided for cleaning the export gas before it is fed to the gas turbine.
- This fine filtering optionally after an upstream dust filtration of the top gas, ensures that an abrasive or Mechanical stress on the gas turbine is avoided and even the finest dusts are deposited.
- An advantageous embodiment of the device according to the invention provides that a compressor for increasing the pressure and / or a cooler for cooling the remaining part of the export gas are provided before it is fed into the device for the separation of CO 2 . This is necessary in order to allow optimal adjustment of the CO 2 capture device and its subsequent use as a reducing gas via appropriate adjustment of the temperature and pressure.
- a fuel gas compressor is provided for compressing the export gas before it is fed to the gas turbine.
- the feed of the gas turbine can be done with the tuned to the gas turbine pressure level.
- an expansion turbine for utilizing the pressure energy of the export gas is provided, wherein the expanded export gas can be supplied via a line of the storage device.
- the pressure energy can be used before the export gas is mixed in the storage device with the tail gas.
- the expansion turbine may be coupled to a generator for generating electricity.
- a special embodiment of the device according to the invention provides that a pre-heating device which can be heated with tail gas is provided for heating the export gas purified of CO 2 , so that the heated, purified export gas can be supplied to the blast furnace.
- a pre-heating device which can be heated with tail gas is provided for heating the export gas purified of CO 2 , so that the heated, purified export gas can be supplied to the blast furnace.
- By burning the tail gas in the heater it is possible to inexpensively heat the purified export gas before it is returned to the blast furnace.
- 1 shows a process schematic of a smelting reduction process with an oxygen-operated blast furnace
- Fig. 2 Scheme process to a smelting reduction process with a with a smelting reduction facility according to COREX ® (lumpy ore) or FINEX ® (fines)
- FIG. 1 shows a blast furnace 1 which is supplied with oxygen via the ring line 2.
- the top gas is supplied via a Topgasabtechnisch 3 a dry separation device 4 and optionally also a Najiabscheidungs observed 5, wherein from the laden with dust top gas, the export gas is formed, which is discharged via the line 6.
- a supply line 7 to the device for the separation of CO 2 8 a part of the export gas is supplied by means of a compressor 9 and a cooler 10 of the device for the separation of CO 2 8, in which case a CO 2 purified export gas, which is also referred to as Recyclegas , And a tail gas are formed, which are discharged via the Recyclegastechnisch 1 1 and the Tailgastechnisch 12 and 13.
- the tail gas line 13 opens into a storage device 14 for receiving the tail gas, resulting in a calorific value compensation in the stored tail gas.
- Tailgaszutechnischen 15a, 15b the pre-stored tail gas can now be supplied to a waste heat steam generator 16.
- steam is generated by combustion of the tail gas, which drives a steam turbine 17 and a generator 18, wherein power is generated.
- the tail gas can also be used to heat the recycled export gas, the tail gas is fed to a preheater 19, in which the tail gas is burned and recycle gas is heated, the heated recycle gas then via a supply line 20 in the blast furnace 1 is introduced.
- the preheating device can also be bypassed and the recycle gas and introduced via a supply line 20a directly into the blast furnace.
- the export gas is primarily used as an energy source, whereby the chemical energy and the pressure energy can be used.
- the export gas is supplied to a buffer device 21 and a filter 22.
- the control of the most uniform export gas quantity possible and the regulation of a uniform as possible calorific value the latter being adjusted by the addition of metallurgical gas or nitrogen.
- the calorific value of the export gas is measured online in the buffer device and the calorific value is raised by adding metallurgical gas or natural gas or lowered by the addition of nitrogen or water vapor.
- the thus treated export gas is added via a fuel gas compressor 23 of the combustion chamber of a gas turbine 24, which in turn drives a generator 25.
- the resulting hot exhaust gas is supplied via exhaust pipes 26 of the waste heat steam generation 16 for generating steam, wherein the steam is in turn processed in the steam turbine 17.
- part of the export gas or even the major part of the export gas can be fed to an expansion turbine 27, this turbine being coupled to a generator (not shown).
- the expanded export gas can then be supplied to the storage device 14, in which then the expanded export gas is mixed with the tail gas.
- Fig. 2 is an analog to Fig. 1 plant or a process scheme, so that the same components have been designated with the same item numbers.
- the smelting reduction process is carried out in a smelting unit 28 and at least one reduction unit R.
- the smelting unit 28 is designed as a melter gasifier.
- the reduction units are guided in countercurrent to the starting materials and withdrawn after use in the reduction units on the last reduction unit R4 as the top gas and purified in a wet separation device 5.
- the now purified top gas can analogously to the description of Figure 1 as export gas of the gas turbine 23 or the device for the separation of CO 2 8 are supplied.
- the tail gas is in turn supplied to the storage device 14 via the tail gas line 12.
- the purified export gas which is also referred to as recycle gas, can be fed via the recycle gas line 11 to the generator gas dedusting device 29.
- the generator gas generated in the melting unit 28 using carbon carriers is dedusted and fed to the reduction unit R1 as process gas or as reducing gas.
- the at least partially reduced material in the reduction units is referred to as low-reduced iron (LRI) and used after agglomeration in the melting unit 28, where it is then melted into pig iron or steel precursors.
- LRI low-reduced iron
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09736395A EP2350323B1 (en) | 2008-10-23 | 2009-09-29 | Method and device for operating a smelting reduction process |
JP2011532564A JP2012506487A (en) | 2008-10-23 | 2009-09-29 | Method and apparatus for performing a smelting reduction method |
CN200980142093.9A CN102203298B (en) | 2008-10-23 | 2009-09-29 | For running the method and apparatus of smelting reduction process |
US13/125,691 US8834599B2 (en) | 2008-10-23 | 2009-09-29 | Method and device for operating a smelting reduction process |
UAA201105110A UA104435C2 (en) | 2008-10-23 | 2009-09-29 | method and device for operating a smelting reduction process |
BRPI0919615A BRPI0919615A2 (en) | 2008-10-23 | 2009-09-29 | method and device for operating a foundry reduction process |
RU2011120330/02A RU2515974C2 (en) | 2008-10-23 | 2009-09-29 | Method and device for control of process of reduction smelting |
AU2009306565A AU2009306565B2 (en) | 2008-10-23 | 2009-09-29 | Method and device for operating a smelting reduction process |
CA2741607A CA2741607A1 (en) | 2008-10-23 | 2009-09-29 | Method and device for operating a smelting reduction process |
US14/465,375 US9574247B2 (en) | 2008-10-23 | 2014-08-21 | Method and device for operating a smelting reduction process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0165808A AT507525B1 (en) | 2008-10-23 | 2008-10-23 | METHOD AND DEVICE FOR OPERATING A MELT REDUCTION PROCESS |
ATA1658/2008 | 2008-10-23 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/125,691 A-371-Of-International US8834599B2 (en) | 2008-10-23 | 2009-09-29 | Method and device for operating a smelting reduction process |
US14/465,375 Division US9574247B2 (en) | 2008-10-23 | 2014-08-21 | Method and device for operating a smelting reduction process |
Publications (1)
Publication Number | Publication Date |
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WO2010046211A1 true WO2010046211A1 (en) | 2010-04-29 |
Family
ID=41396433
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2009/062607 WO2010046211A1 (en) | 2008-10-23 | 2009-09-29 | Method and device for operating a smelting reduction process |
Country Status (14)
Country | Link |
---|---|
US (2) | US8834599B2 (en) |
EP (1) | EP2350323B1 (en) |
JP (1) | JP2012506487A (en) |
KR (1) | KR101610661B1 (en) |
CN (1) | CN102203298B (en) |
AR (1) | AR073960A1 (en) |
AT (1) | AT507525B1 (en) |
AU (1) | AU2009306565B2 (en) |
BR (1) | BRPI0919615A2 (en) |
CA (1) | CA2741607A1 (en) |
RU (1) | RU2515974C2 (en) |
TW (1) | TW201016857A (en) |
UA (1) | UA104435C2 (en) |
WO (1) | WO2010046211A1 (en) |
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AT509224A4 (en) * | 2010-05-20 | 2011-07-15 | Siemens Vai Metals Tech Gmbh | METHOD AND DEVICE FOR CONTROLLING THE TEMPERATURE OF PROCESS GASES FROM PLANTS FOR THE PRODUCTION OF REPRODUCTION FOR THE USE OF A RELAXATION TURBINE |
WO2012095329A3 (en) * | 2011-01-13 | 2012-09-07 | Siemens Aktiengesellschaft | Method for treating a carbon dioxide-containing waste gas from an electrofusion process |
WO2012123320A1 (en) * | 2011-03-17 | 2012-09-20 | Siemens Vai Metals Technologies Gmbh | Metallurgical plant with efficient waste-heat utilization |
WO2012175313A1 (en) * | 2011-06-21 | 2012-12-27 | Siemens Vai Metals Technologies Gmbh | Device for the closed-loop control of process gases in a plant for producing directly reduced metal ores |
US8834599B2 (en) | 2008-10-23 | 2014-09-16 | Siemens Vai Metals Technologies Gmbh | Method and device for operating a smelting reduction process |
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Also Published As
Publication number | Publication date |
---|---|
US20140361472A1 (en) | 2014-12-11 |
KR101610661B1 (en) | 2016-04-08 |
US8834599B2 (en) | 2014-09-16 |
AR073960A1 (en) | 2010-12-15 |
AT507525B1 (en) | 2010-09-15 |
AU2009306565A1 (en) | 2010-04-29 |
CA2741607A1 (en) | 2010-04-29 |
EP2350323A1 (en) | 2011-08-03 |
JP2012506487A (en) | 2012-03-15 |
RU2011120330A (en) | 2012-11-27 |
CN102203298A (en) | 2011-09-28 |
TW201016857A (en) | 2010-05-01 |
AT507525A1 (en) | 2010-05-15 |
RU2515974C2 (en) | 2014-05-20 |
EP2350323B1 (en) | 2013-01-23 |
UA104435C2 (en) | 2014-02-10 |
KR20110075033A (en) | 2011-07-05 |
US9574247B2 (en) | 2017-02-21 |
US20110283837A1 (en) | 2011-11-24 |
CN102203298B (en) | 2015-09-23 |
BRPI0919615A2 (en) | 2015-12-08 |
AU2009306565B2 (en) | 2014-02-13 |
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